The first-principles (ab initio) computation of potential energy surfaces during real-time molecular dynamics and equlibrium sampling holds tremendous power for the simulation of reactive chemical complexes. The application of these powerful methods is often limited, however, by the relatively enormous cost of ab initio calculations.In this work, we present multiple avenues to address this cost and to enable the simulation of larger chemical systems. In particular, we develop several methods at the interface of electronic structure theory and sampling/dynamics. Recent advancements include multiple-timestep ab initio molecular dynamics, in which key pieces of standard electronic structure theory approaches are updated on differing timescales. Similar progress in the simulation of quantum mechanical nuclear motion via path integral sampling will also be described. The resulting methods demonstrate computational speedups ranging from a factor of two to many orders of magnitude, with little or no approximation.Demonstration of these new methods in the context of water-splitting chemistry, ion solvation, and other reactive complexes�where electronic structure theory is most relevant�will be presented.

Accelerated ab initio sampling and molecular dynamics

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.